[0001] The present invention relates to a multilayer polyolefinic film having excellent
mechanical properties, good processability and improved tear resistance after self
heat sealing.
[0002] More specifically, the present invention relates to a multilayer film comprising
a main layer based on a polymer or copolymer of propylene, on at least one surface
of which, (preferably on both), at least a second layer essentially consisting of
a mixture of a polymer or copolymer of propylene with a particular copolymer of ethylene,
is laid, normally by means of co-extrusion.
[0003] Films based on polyolefins are widely used in packaging operations of a great variety
of products. The properties normally requested for these films are transparency, mechanical
and environmental resistance, gloss, heat shrinking and good self-seal. In particular,
a good self-seal means that the film must be sealable on itself by means of high rate
linear sealing devices, so as not to slow down the productive chain from which the
product, already packaged, leaves, ready for shipment.
[0004] Prevalently isotactic polypropylene, or copolymers of propylene containing up to
10% by weight of a second olefinic monomer, preferably ethylene, have satisfactory
mechanical and optical properties for the above purposes and can be processed to give
films appropriate for many uses. Films made of polypropylene or its copolymers, however,
are not sufficiently self-sealing, and the packaging obtained therewith tends to tear
easily along the welding lines.
[0005] It has been found that polyethylene and, particularly, copolymers of ethylene with
1-butene normally known as LLDPE, on the contrary, have a satisfactory self-seal but
they do not give films with satisfactory mechanical and optical properties for certain
uses. Films consisting of two or more different polymeric layers are also described
in literature, in which, for example, a polypropylene film is co-extruded with a polyethylene
film to obtain a bi-layered film easily sealable onto the surface of polyethylene
and having the typical mechanical characteristics of polypropylene. For example, U.S.
patent 4,565,738 describes a film comprising an internal layer of polypropylene on
whose surfaces two finer layers of a composition comprising a propylene/ethylene block
copolymer and a copolymer of ethylene with an alpha-olefin, are co-extruded. These
films, however, still have unsatisfactory optical properties and tend to have detachment
areas between the two polymeric layers, owing to the poor adherence between polyethylene
and polypropylene, especially in those applications in which the stretching conditions
to which the film is subjected before use, are particularly severe.
[0006] Another particularly critical problem relates to the minimum temperature at which
the self-sealing operation can be effected. In fact, it is preferable for the sealing
between two edges or surfaces of a film to be carried out at a relatively low temperature
(possibly < 120°C) without there being any deterioration in the mechanical properties
of the sealing itself, particulary the tensile strength and tear resistance. In fact,
the lower the sealing temperature, with the same mechanical resistance, the greater
is the rate at which it is possible to operate in industrial processes for the manufacturing
of products for packaging.
[0007] It has generally been found that an improvement in the performance of films for the
above uses can be obtained by arranging two or more layers co-extruded with each other
to form a multilayer film in which at least one layer (usually high-melting) gives
the desired mechanical properties, whereas a suitable surface layer allows the sealing
to be effected at lower temperatures. There are numerous parameters however which
must be taken into consideration in the production of these multilayer films to obtain
a really satisfactory product which is suitable for the greatest number possible of
industrial demands. It is necessary in fact for the layers in the film to have excellent
adherence with each other without requiring the use of glues. In addition the film
must have a sufficient transparency and a good surface appearance without defects
or heterogeneous areas. It should also be possible to subject the film to mono or
bidimensional stretching without part of the layers becoming detached, as well as,
naturally, a good self-seal and mechanical resistance as specified above.
[0008] The Applicant has now found that by using a particular polymeric composition to produce
a self-sealing layer of a multilayer film, it is possible to obtain an excellent combination
of the various properties described above, to produce a film with a good transparency
and surface gloss, excellent adhesion between the layers, reduced self-sealing temperature
and excellent mechanical properties.
[0009] The present invention therefore relates to a multilayer film comprising:
(A) at least one polymeric layer essentially consisting of a crystalline polymer of
propylene or a composition of said crystalline polymer with up to 10% by weight of
a polymer of ethylene;
(B) at least one polymeric layer co-extruded with the previous one, essentially consisting
of a composition of:
(a) from 65 to 99% by weight of a statistic copolymer of propylene containing from
0.5 to 20%, preferably from 1 to 10%, in moles of monomeric units deriving from ethylene;
(b) from 1 to 35% by weight of a copolymer of ethylene containing from 1 to 10% in
moles of monomeric units deriving from an alpha-olefin having at least 5, preferably
from 6 to 12, carbon atoms.
[0010] The term "essentially consisting of", as used in the present description and claims
with reference to the composition of polymeric layers or film, means that a certain
layer or film may also comprise, in addition to the polymer or specific composition,
optional additives normally used in the art, such as antioxidants, slip agents, anti-flame
plasticizers, etc., which are not present in a quantity exceeding 5% by weight.
[0011] The term "polymer of", when referring to a certain monomer, also comprises in its
definition, unless otherwise specified, the meaning of "copolymer" of that monomer
which forms the most abundant monomeric unit thereof.
[0012] In its more general aspect, the present invention relates to a multilayer film consisting
of at least two layers (A) and (B) as defined above. Films consisting of three or
more layers, in which at least two layers can be identified of the type (A) and (B)
respectively, adjacent and co-extruded, of which layer (B) forms at least an external
surface, are therefore included in the scope of the present invention.
[0013] In a particularly preferred embodiment of the present invention, a layer (A) as defined
above is placed between two layers (B), preferably having the same composition, each
co-extruded on a surface of layer (A), so as to form a three-layered film in which
the thickness of the central layer (A) measures from 50 to 90% of the total thickness
of the film.
[0014] According to the present invention, the crystalline polymer of propylene suitable
as main constituent of layer (A) is selected from homo-polymers and co-polymers of
propylene, or their mixtures, obtained by the known stereospecific polymerization
processes also called "Ziegler-Natta". More recently these polymers have also been
obtained by means of processes which use catalysts based on metallocenes of titanium
or zirconium, and also other complexes of transition metals. The main characteristic
of these polymers is the presence in the polymeric chain of more or less long sequences
of chiral monomeric units deriving from propylene, all having the same configuration
or an alternating configuration according to a non-random rule. Typical polymers of
this type are isotactic polypropylene, commercially available in numerous grades and
types, in addition to syndiotactic polypropylene and copolymers of propylene with
other alpha-olefins, particularly copolymers of propylene with ethylene 1-butene,
1-hexene, 1-pentene, 1-octene, containing 10% of alpha-olefin at the most. In order
to obtain a satisfactory mechanical performance for a high number of uses, the above
polymers of propylene preferably have a Melt Flow Index, abbr. MFI, measured according
to the ISO 1133 method) ranging from 0.2 to 5.0 g/10 min.
[0015] Particularly preferred for layer (A) are prevalently isotactic homopolymers of propylene
with an MFI ranging from 1.5 to 2.5 g/10min and a tacticity degree (iso dyads/syndio
dyads) of more than 90%.
[0016] According to a particular embodiment of the present invention, layer (A) essentially
consists of a composition of a polymer of propylene as defined above, preferably polypropylene
homopolymer, with from 1 to 5% by weight (with respect to the total weight of the
composition) of a copolymer of ethylene, preferably a copolymer of ethylene containing
from 1 to 10% in moles of monomeric units deriving from an alpha-olefin having from
3 to 12 carbon atoms, more preferably of the same copolymer selected as component
(b) of layer (B).
[0017] As far as layer (B) is concerned, this preferably consists of a composition of (a)
and (b), as previously defined, in weight ratios ranging from 90/10 to 70/30. In fact
in this composition range, an excellent equilibrium between transparency, sealing
and adherence to layer (A) is obtained, even though ratios not included therein can
conveniently be used when the expert in the field wishes to give privilege to particular
characteristics with respect to others.
[0018] The copolymer of propylene which forms component (a) of the present invention is
a statistic copolymer ("random" according to the English term commonly used in the
art) of propylene with from 0.5 to 20% in moles of monomeric units deriving from ethylene,
or a mixture of these copolymers. It has been found however that the best results
with respect to the adhesion properties to layer A and sealing properties, are obtained
with these copolymers of propylene containing from 1 to 10%, more preferably from
1 to 5% in moles of ethylene units. These copolymers can also be obtained with the
known polymerization processes in the presence of Ziegler-Natta type catalysts, including
catalysts based on a complex of a transition metal, particularly a metallocene of
titanium or zirconium. In these processes, a gaseous or liquid (under pressure) mixture
of propylene and ethylene in the appropriate proportions is fed to a reactor in which
it comes into contact with the catalyst and produces the desired copolymer. As can
be observed from infra-red spectroscopic and NMR analyses, the monomeric units deriving
from ethylene are distributed at random along the whole polymeric chain.
[0019] The polymer which forms component (b) of layer (B) of the present invention is selected
from linear copolymers of ethylene with at least one alpha-olefin having at least
5 carbon atoms, or their mixtures. Preferred alpha-olefins are those non-branched
having from 6 to 10 carbon atoms, such as, for example, 1-hexene, 1-octene, 1-decene,
all commercially available in industrial quantities. These copolymers of ethylene
belong to the known group of linear low density polyethylene (LLDPE or VLDPE) and
contain from 1 to 10% in moles, in total, of monomeric units deriving from one or
more of said alpha-olefins. Monomeric units deriving from lower alpha-olefins, such
as propylene or 1-butene, may also be present in the copolymer forming component (b),
provided they are in a quantity not exceeding 5% in moles, without jeopardizing the
advantageous properties thereof for the purposes of the present invention. Typically,
the polymer forming component (b) has an MFI ranging from 3.1 to 5.5 g/10 min. and
a density, measured according to the ISO 1183 method, ranging from 0.89 to 0.93. Also
these copolymers, like the previous ones, can be obtained with the known polymerization
techniques in the presence of Ziegler-Natta catalysts or catalysts based on complexes
of transition metals. In general, any expert in the field is capable of determining,
in the project phase, the optimum polymerization conditions and type of catalyst for
obtaining the desired polyethylene, which may vary from those preselected for obtaining,
for example, the polymer of propylene suitable as constituent of component (a) described
above. Polymers of ethylene suitable as component (b) of the present invention are
commercially available at various suppliers, for example, Polimeri Europa S.r.l. under
the trade-name of CLEARFLEX®.
[0020] The composition forming layer (B) (and, if the case, forming layer (A)) can be prepared
prior to the preparation process of the multilayer film, by mixing, in the molten
state, the established quantities of the two components (a) and (b), until a homogeneous
mixture is formed. This can be easily effected in particular equipment suitable for
the purpose and known to experts in the field. Particularly, the two components can
be dry premixed and subsequently melted and homogeneously mixed with each other in
extruders operating according to the known techniques and conditions, under the force
of one or more appropriately shaped screw shafts. Alternatively the two components,
normally in granule form, can be fed separately in different points of the extruder
by means of hoppers. At the end, the composition thus obtained is expelled in the
form of a thread having a diameter of about 5 mm, cooled and solidified and finally
cut into granule form. The polymeric composition of layer (B) thus obtained can be
conserved for an indefinite period before being melted again in equipment for the
preparation of the co-extruded film. This equipment usually comprises two or more
extrusion systems (slotted sleeve extruder and gear pump), depending on the desired
number of layers with a different composition, connected to a particular ring nozzle
from whose end, subdivided into separate channels, the layers of polymer in the molten
state emerge and immediately converge with each other, in continuous. The multilayer
thus formed, still semi-molten, is then expanded and cooled under the pressure of
an airjet, according to the known "blow-extrusion" technique. Alternatively, the components
for the composition of layer (B) can be directly fed to the extruder connected with
the above nozzle. In this way, the multilayer film of the present invention is obtained,
in continuous, starting from the single polymeric components. Equipment suitable for
the purpose is easily available on the market.
[0021] The multilayer film thus obtained normally has a thickness, depending on the specific
requirements, ranging from 10 to 500 µm, although films with a thickness outside this
range are also included in the present invention, the thickness of the film not being
a critical element thereof. The film is subsequently mono- or bi-dimensionally stretched,
finally obtaining the desired thickness (usually 5-100 µm) and mechanical properties,
before its commercial use. As already mentioned, the thickness of the layer (or layers)
of type (A) form, in all, from 50 to 90%, preferably from 60 to 80% of the total thickness
of the film, whereas the layer (or layers) of type (B) form, in all, at least 5%,
preferably at least 15% and more preferably from 15 to 30% of the total thickness
of the film in question.
[0022] The multilayer film of the present invention is characterized by a low minimum heat
sealing temperature, measured according to the method described hereunder, ranging,
according to the composition of layer (B), from 105 to 115°C, for a stress resistance
of at least 1000 cN/cm. This desirable property is surprisingly obtained without any
damage at all to the other properties such as transparency, gloss and adherence between
the layers of film (especially during the stretching). The film thus conserves excellent
optical properties, comparable to those of polypropylene film alone, in addition to
an excellent self-consistency and a high tear and delamination resistance.
[0023] The multilayer films of the present invention can be used for a wide variety of industrial
applications, mainly in the field of flexible packaging and adhesive tapes such as,
for example, no-collant thermoshrinkable and biorientated.
[0024] Some illustrative examples are provided hereunder for a more detailed description
of the present invention and for its embodiment, which however do not form any limitation
whatsoever to the scope of the present application and relative patent.
[0025] The following polymeric materials were used in the examples for the preparation of
the multilayer film:
P1) random propylene-ethylene copolymer produced by MONTELL S.p.A. under the trade-name
of "Adsyl 5 C 37 F"®;
P2) polypropylene homopolymer produced by AMOCO under the trade-name of "BOPP 157
GD02"®;
E1) linear ethylene-1-hexene copolymer (LLDPE-C6) produced by POLIMERI EUROPA S.r.l.
under the trade-name of "Clearflex CL 106"®;
E2) linear ethylene-1-octene copolymer (LLDPE-C8) produced by POLIMERI EUROPA S.r.l.
under the trade-name of (Clearflex CL 508)®.
[0026] The main characteristics of the above polymeric materials are indicated in table
1 below.

The films obtained were subjected to characterization according to the methods listed
hereunder.
- Optical properties:
- HAZE, according to the method ASTM D1003-92;
- gloss AT 45°, according to the method ASTM D 2457-90
- Tensile properties, (according to the method ASTM D 882-91)
- Ultimate tensile stress
- Yield point
- Ultimate elongation
- Heat shrinking properties, according to norm UNI 8515-83
- Sealing with HEAT SEAL, according to the internal method M001-2.73, set up by the
Applicant and described hereunder.
HEAT SEAL.Rectangular test-samples of 300 x 15 mm are prepared of the film on which
the measurement is to be made. Adhesive tape is placed on one side of the film. The
sample thus prepared is first U-folded with the adhesive tape on the outside, and
then inserted between two plates of a sealing apparatus "PACK FORSK HOT TACK TESTER
Mod. 52-B", whose sealing temperature has been preset at the selected value, 110°C
in this case. After effecting the sealing at a pressure of 0.15 MPa for 0.5 seconds,
the test-sample is extracted and left to rest for 24 hours in an environment conditioned
at 23°C and 50% of relative humidity. The ends of the test-sample are then inserted,
under the same conditions, between the clips of an INSTRON dynamometre and subjected
to tensile stress until breakage of the seal. The F break force is recorded and the
"Heat Seal Strength" (HSS) result is expressed as a ratio F/L wherein L is the width
of the test-sample in cm (3 cm).
EXAMPLES 1-5
[0027] 5 samples of three-ply film were prepared by combining the polymers specified above.
In example 1, which should be considered as a comparative reference sample, both the
internal layer and the two external layers essentially consist of polymers of propylene;
in the other examples 2 to 5, the internal layer is of type (A) and the external layers
are the same and consist of a composition of type (B) of the present invention. The
relative compositions of each layer are indicated in table 2 below. These compositions
were obtained by mixing the components, in the suitable proportions, in an extruder,
followed by the blow-extrusion of the multilayer film by means of an appropriate ring
nozzle at the head of the equipment.

[0028] The films were prepared by means of a multilayer minicast plant comprising a "SIMPLAS"
"coathanger" head with an opening of 0.6 mm, a total width of 350 mm and a useful
film width of 220 mm. Three extruders were connected at the head, one for each polymeric
layer, having the following characteristics:
Extruder for: |
Trade-mark |
Screw diam. (mm) |
length/diam. |
extern.layer |
GHIOLDI |
30 |
27 |
central layer |
GHIOLDI |
30 |
27 |
extern. layer |
GOETTFERT |
35 |
27 |
The operating conditions are indicated in table 3:

[0029] At the end of each preparation, the non-stretched film was characterized by measuring
its properties according to what is listed above. The results of the characterization
tests are indicated in table 4 below.
Table 4
Film properties |
Property |
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5 |
Gloss 45° |
82.1 |
59.0 |
52.9 |
56.1 |
48.6 |
HAZE (%) |
3.0 |
8.1 |
9.8 |
10.2 |
14.5 |
HEAT SEAL at 110° (cN/m) |
616 |
1169 |
1241 |
823 |
964 |
Test direction |
MD |
TD |
MD |
TD |
MD |
TD |
MD |
TD |
MD |
TD |
Yield point (N/mm2) |
20.1 |
17.3 |
22.5 |
18.7 |
22.8 |
20.8 |
26.6 |
24.1 |
25.2 |
18.8 |
Breaking load (N/mm2) |
42.4 |
10.7 |
51.7 |
25.4 |
52.4 |
25.1 |
49.9 |
19.5 |
49.9 |
9.8 |
Ultimate elongation (%) |
400 |
140 |
450 |
540 |
460 |
500 |
425 |
275 |
445 |
57 |
Secant modulus 1% (N/mm2) |
344 |
319 |
369 |
395 |
395 |
382 |
448 |
446 |
441 |
480 |
Heat shrinkage (170°C/10s) (%) |
74 |
0 |
80 |
0 |
78 |
0 |
76 |
0 |
80 |
0 |
MD = Test carried out on the film in the same stretching direction |
TD = Test carried out on the film transversally to the stretching direction |
1. A multilayer film comprising:
(A) at least one polymeric layer essentially consisting of a crystalline polymer of
propylene or a composition of said crystalline polymer with up to 10% by weight of
a polymer of ethylene;
(B) at least one polymeric layer co-extruded with the previous one, essentially consisting
of a composition of:
(a) from 65 to 99% by weight of a statistic co-polymer of propylene containing from
0.5 to 20% in moles of monomeric units deriving from ethylene;
(b) from 1 to 35% by weight of a copolymer of ethylene containing from 1 to 10% in
moles of monomeric units deriving from an alpha-olefin having at least 5 carbon atoms.
2. The multilayer film according to claim 1, consisting of three co-extruded layers in
which a central layer (A) is placed between two external layers (B), so that the thickness
of the central layer (A) measures from 50 to 90% of the total thickness of the film.
3. The multilayer film according to claim 2, wherein the two external layers (B) have
the same thickness and composition.
4. The multilayer film according to any of the previous claims, wherein said alpha-olefin
in the copolymer of ethylene which forms component (b) is selected from linear alpha
olefins having from 6 to 10 carbon atoms.
5. The multilayer film according to any of the previous claims, wherein said statistic
copolymer of propylene which forms component (a) comprises from 1 to 10% preferably
from 1 to 5%, in moles of monomeric units deriving from ethylene.
6. The multilayer film according to any of the previous claims, wherein said layer (A)
essentially consists of prevalently isotactic polypropylene.
7. The multilayer film according to any of the previous claims from 1 to 5, wherein said
layer (A) essentially consists of a composition containing prevalently isotactic polypropylene
and from 1 to 5% by weight of the same copolymer of ethylene which forms component
(b) of said layer (B).
8. The multilayer film according to any of the previous claims, wherein, in said layer
(B), components (a) and (b) are present in a weight ratio ranging from 90/10 to 70/30.
9. The multilayer film according to any of the previous claims, having a total thickness,
when not stretched, ranging from 10 to 500 µm.
10. Mono- or bi-orientated film according to any of the previous claims from 1 to 9.
11. Use of the film according to any of the previous claims for the production of flexible
packaging and adhesive tapes.